Benzotriazoles, and their production and use 4-halophenyl-tetrahydrobenzotriazloes as herbicides

ABSTRACT

A compound of the formula: ##STR1## wherein R is a hydrogen atom, a C 1  -C 4  alkoxy group, a C 1  -C 4  alkenyloxy group, a C 3  -C 4  alkynyloxy group, a C 1  -C 4  alkylthio group, a dichlorocyclopropylmethoxy group or a methyldichlorocyclopropylmethoxy group, X is a chlorine atom or a bromine atom and Y is a hydrogen atom, a fluorine atom or a chlorine atom, which is useful as a herbicide.

The present invention relates to4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxides (hereinafter referred toas "benzotriazoles"), and their production and use.

Said benzotriazoles are representable by the formula: ##STR2## wherein Ris a hydrogen atom, a C₁ -C₄ alkoxy group, a C₃ -C₄ alkenyloxy group, aC₃ -C₄ alkynyloxy group, a C₁ -C₄ alkylthio group, adichlorocyclopropylmethoxy group or a methyldichlorocyclopropylmethoxygroup, X is a chlorine atom or a bromine atom and Y is a hydrogen atom,a fluorine atom or a chlorine atom.

It has now been found that the benzotriazoles (I) show a strongherbicidal activity against a wide variety of weeds includingbroad-leaved weeds, Graminaceous weeds, Commelinaceous weeds andCyperaceous weeds in agricultural plowed fields by foliar or soiltreatment and do not produce any material phytotoxicity on variousagricultural crops (i.e. corn, wheat, rice plant, soybean, cotton,sugarbeet). Examples of broad-leaved weeds which can be controlled orexterminated by the benzotriazoles (I) are wild buckwheat (Polygonumconvolvulus), pale smartweed (Polygonum lapathifolium), common purslane(Portulaca oleracea), common lambsquarters (Chenopodium album), redrootpigweed (Amaranthus retroflexus), garden radish (Raphanus sativus), wildmustard (Sinapis arvensis), shepherdspurse (Capsella bursa-pastoris),hemp sesbania (Sesbania exaltata), sickle-pod (Cassia tora), velvetleaf(Abutilon theophrasti), prickly sida (Sida spinosa), field pansy (Violaarvensis), ivyleaf morningglory (Ipomoea hederifolia), tall morningglory(Ipomoea purpurea), field bindweed (Convolvulus arvensis), reddeadnettle (Lamium purpureum), henbit (Lamium amplexicaure), jimsonweed(Datura stramonium), black nightshade (Solanum nigrum), birdseyespeedwell (Veronica persica), ivyleaf speedwell (Veronica hederaefolia),heartleaf cocklebur (Xanthium strumarium), common sunflower (Helianthusannuus), scentless chamomile (Matricaria inodola), corn marigold(Chrysnathemum segetum), etc. Examples of Graminaceous weeds againstwhich the benzotriazoles (I) show a herbicidal activity are Japanesemillet (Echinochloa frumentacea), common barnyardgrass (Echinochloacrus-galli), green foxtail (Setaria viridis), large crabgrass (Digitariasanguinalis), annual bluegrass (Poa annua), blackgrass (Alopecurusmyosuroides), common oat (Avena sativa), wild oat (Avena fatua ),Johnsongrass (Sorghum halepense), downy brome (Bromus tectorum), etc.Examples of Commelinaceous weeds are asiatic dayflower (Commelinacommunis), etc. Examples of Cyperaceous weeds are rice flatsedge(Cyperus iria), etc. It has also been found that the benzotriazoles (I)can control or exterminate in paddy fields broad-leaved weeds such ascommon falsepimpernel (Lindernia procumbens), toothcup (Rotala indica),waterwort (Elatine triandra), Graminaceous weeds such as barnyardgrass(Echinochloa oryzicola), Cyperaceous weeds such as smallflower sedge(Cyperus difformis), hardstem bulrush (Scirpus juncoides), slenderspikerush (Eleocharis acicularis), nutsedge (Cyperus serotinus) andpaddy-field weeds such as pickerelweed (Monochoria vaginalis), arrowhead(Sagittaria pygmaea), waterplantain (Alisma canaliculatum), whileexerting no material phytotoxicity to rice plants. Accordingly, thebenzotriazoles (I) can be used as herbicides applicable to agriculturalplowed fields as well as paddy fields without exerting any materialchemical injury to soybean and rice plants.

Among the benzotriazoles (I) of the present invention, those wherein Ris a C₁ -C₄ alkoxy group, a C₃ -C₄ alkenyloxy group or a C₃ -C₄alkynyloxy group, X is a chlorine atom or a bromine atom and Y is ahydrogen atom or a fluorine atom are preferred. Particularly preferredare2-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide,2-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide,2-(4-chloro-2-fluoro-5-allyloxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide,etc.

The benzotriazoles (I) of the present invention may be prepared by thefollowing procedures:

Procedure (a)

The benzotriazole of the formula: ##STR3## wherein R₁ is a hydrogenatom, a C₁ -C₄ alkoxy group or a C₁ -C₄ alkylthio group and X and Y areeach as defined above is obtainable by subjecting a2-phenylhydrazonocyclohexanone oxime of the formula: ##STR4## whereinR₁, X and Y are each as defined above to ring closure, i.e. reactingwith an oxidizing agent in a solvent at a temperature of 0° to 100° C.for a period of 0.5 to 10 hours.

As the solvent, there may be used aliphatic hydrocarbons (e.g. hexane,heptane), aromatic hydrocarbons (e.g. benzene, toluene, xylene),halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride,dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. dioxane,tetrahydrofuran, diethylene glycol dimethyl ether), alcohols (e.g.ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methylcellosolve, diethylene glycol, glycerol), esters (e.g. ethyl formate,ethyl acetate, butyl acetate, diethyl carbonate), nitriles (e.g.acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine,triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine),acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), ammoniawater, water, etc. They may be employed alone or in combination.

Examples of the oxidizing agent are mercury oxide, lead tetraacetate,cupric salts (e.g. cupric sulfate). The use of an aqueous solution ofcupric sulfate in the presence of pyridine is particularly preferred.The amount of the oxidizing agent may be usually from 1 to 1.5equivalents to the 2-phenylhydrazinocyclohexanone oxime (II).

After completion of the reaction, the reaction mixture may be subjectedto post-treatment such as extraction with an organic solvent orconcentration to obtain the objective compound (I-a). If necessary,purification by chromatography or recrystallization may be adopted.

Procedure (b)

The benzotriazole of the formula: ##STR5## wherein R₂ is a C₁ -C₄ alkoxygroup, a C₃ -C₄ alkenyloxy group, a C₃ -C₄ alkynyloxy group, adichlorocyclopropylmethoxy group or a methyldichlorocyclopropylmethoxygroup and X and Y are each as defined above is obtainable by reacting a2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide of theformula: ##STR6## wherein X and Y are each as defined above with acompound of the formula:

    R.sub.2 --Z                                                (IV)

wherein Z is a halogen atom, an alkyl-substituted phenylsulfonate groupor an alkylsulfonate group and R₂ is as defined above in a solvent inthe presence of a dehydrohalogenating agent at a temperature of 0° to150° C. for a period of 0.5 to 24 hours. If necessary, a phase transfercatalyst may be present in the reaction system.

The amounts of the compound (IV), the dehydrohalogenating agent and thephase transfer catalyst may be respectively from 1.0 to 1.5 equivalents,from 1.0 to 1.5 equivalents and from 0.01 to 0.1 equivalent to thecompound (III).

As the solvent, there may be exemplified aromatic hydrocarbons (e.g.benzene, toluene, xylene), ketones (e.g. acetone, methyl ethyl ketone),amides (dimethylformamide, dimethylacetamide), sulfoxides (e.g.dimethylsulfoxide), ethers (e.g. tetrahydrofuran, diethyl ether,ethylene glycol dimethyl ether), nitriles (e.g. acetonitrile), water,etc. These may be used solely or in combination.

Examples of the dehydrohalogenating agent are inorganic bases (e.g.sodium carbonate, potassium carbonate, sodium hydroxide, potassiumhydroxide), organic bases (e.g. pyridine, triethylamine,N,N-dimethylaniline, N,N-diethylaniline), etc.

As the phase transfer catalyst, there may be used tetrabutylammoniumbromide, tributylbenzylammonium chloride, triethylbenzylammoniumbromide, etc. Further, potassium iodide or a monovalent copper salt isoccasionally added as a reaction accelerator.

After completion of the reaction, the reaction mixture may be subjectedto post-treatment such as extraction with an organic solvent orconcentration to obtain the objective compound (I-b). If necessary,purification by chromatography or recrystallization may be adopted.

Practical and presently preferred embodiments for production of thebenzotriazoles (I) are illustratively shown in the following Examples.

EXAMPLE 1 (Procedure (a))

To a solution of 2-(4-chlorophenylhydrazono)cyclohexanone oxime (1.6 g)in a mixture of 15% aqueous solution of pyridine (25 ml) andtetrahydrofuran (20 ml), a solution of cupric sulfate (CuSO₄.5H₂ O) (2.5g) in water (10 ml) was added at room temperature, and the resultantmixture was heated under reflux for 2 hours. After cooling, water wasadded to the mixture, which was then extracted with ethyl acetate. Theextract was washed with a saturated aqueous cupric sulfate solution andwater in order, dried and concentrated. The residue was purified bysilica gel column chromatography using a mixture of n-hexane and ethylacetate as an eluent to give 0.2 g of2-(4-chlorophenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide(Compound No. 1). M.P., 100°-101° C.

EXAMPLE 2 (Procedure (b))

To a mixture of2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide(1 g), potassium carbonate (0.3 g) and dimethylformamide (5 ml),propargyl bromide (0.6 g) was added, and the resultant mixture wasstirred at 70° to 80° C. for 4 hours. After cooling, water was added tothe mixture, which was then extracted with ethyl acetate. The organiclayer was washed with water, dried and concentrated. The residue waspurified by silica gel thin layer chromatography using a mixture ofn-hexane and ethyl acetate as a developing solvent to give 0.15 g of2-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide(Compound No. 12). M.P., 155°-156° C.

In the same manner as above, there are produced the benzotriazoles (I),of which some typical examples are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                         ##STR7##                     (I)                                             Compound                                                                      No.     X     Y     R            Physical constant                            ______________________________________                                        1       Cl    H     H            M.P. 100-101° C.                      2       Cl    F     H            M.P. 146-146.5° C.                    3       Cl    H     iso-C.sub.3 H.sub.7 O                                                                      M.P. 108-109° C.                      4       Cl    H     C.sub.2 H.sub.5 O                                                                          Glassy                                       5       Cl    F     CH.sub.3 O   M.P. 120-122° C.                      6       Cl    F     n-C.sub.3 H.sub.7 O                                                                        M.P. 61-61.5° C.                      7       Cl    F     iso-C.sub.3 H.sub.7 O                                                                      M.P. 109-109.8° C.                    8       Cl    Cl    iso-C.sub.4 H.sub.9 O                                                                      M.P. 100-101° C.                      9       Cl    F     iso-C.sub.3 H.sub.7 S                                                                      M.P. 89-91° C.                        10      Br    H     H            M.P. 102-103° C.                      11      Cl    H     HCCCH.sub.2 O                                                                              M.P. 136-137° C.                      12      Cl    F     HCCCH.sub.2 O                                                                              M.P. 155- 156° C.                     13      Cl    F                                                                                    ##STR8##    n.sub.D.sup.24 1.5668                        14      Cl    F     H.sub.2 CCHCH.sub.2 O                                                                      n.sub.D.sup.24 1.5732                        15      Cl    F                                                                                    ##STR9##    M.P. 73-74° C.                        16      Cl    F                                                                                    ##STR10##   Glassy                                       ______________________________________                                    

The 2-phenylhydrazonocyclohexanone oxime (II), i.e. the startingmaterial for production of the compound (I-a), may be prepared byreacting a phenylhydrazine compound of the formula: ##STR11## whereinR₁, X and Y are each as defined above with a 1.0 to 1.1 equivalentamount of a cyclohexene compound of the formula: ##STR12## wherein Q₁and Q₂ are, the same or different, each a lower alkyl group or, whentaken together with the nitrogen atom to which they are attached, theymay form a ring containing or not an oxygen atom in a solvent in thepresence of a catalytic amount of an acid at a temperature of 0° to 100°C. for a period of 0.5 to 12 hours.

As the acid, there may be used acetic acid, dilute hydrochloric acid orthe like. Examples of the solvent are methanol, ethanol, ethylene glycolmonomethyl ether, ethylene glycol, etc.

Upon completion of the reaction, the reaction mixture is subjected topost-treatment such as extraction with an organic solvent orconcentration to obtain the 2-phenylhydrazonocyclohexanone oxime (III).If necessary, the purification by chromatography or recrystallizationmay be adopted.

A typical example for production of the 2-phenylhydrazonocyclohexanoneoxime (II) is as follows:

EXAMPLE 3

p-Chlorophenylhydrazine (1.42 g) was added to a mixture ofN-(2-hydroxyimino-1-cyclohexenyl)morpholine (1.96 g) and ethanol (15 ml)containing a catalytic amount of acetic acid, and the resultant mixturewas heated under reflux for 3 hours. After cooling, ethanol was removedfrom the mixture by distillation under reduced pressure, and water wasadded thereto, followed by extraction with ethyl acetate. The organiclayer was washed with water, dried and concentrated. The residue waspurified by silica gel column chromatography using a mixture of n-hexaneand ethyl acetate as an eluent to give 1.6 g of2-(4-chlorophenylhydrazono)cyclohexanone oxime as a red glassy material.

In the same manner as above, there were produced the2-phenylhydrazonocyclohexanone oximes (II), of which typical examplesare shown in Table 2.

                  TABLE 2                                                         ______________________________________                                         ##STR13##                                                                    Compound                                                                      No.     X       Y     R.sub.1   Physical constant                             ______________________________________                                        a       Cl      F     CH.sub.3 O                                                                              M.P. 190-191° C.                       b       Cl      F     iso-C.sub.3 H.sub.7 O                                                                   M.P. 156-156.5° C.                     c       Cl      F     H         M.P. 187-189° C.                                                       (decomp.)                                     ______________________________________                                    

The 2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-benzotriazole-1-oxide (III)as the starting material in production of the benzotriazoles (I-b) isobtainable by reacting a hydrazone compound of the formula: ##STR14##wherein X and Y are each as defined above with a 1.0 to 1.5 equivalentamount of an oxidizing agent in a solvent at a temperature of 0° to 150°C. for a period of 1.0 to 24 hours.

The solvent usable in the reaction are water, tetrahydrofuran, pyridine,ether, etc. These may be used solely or in combination.

Examples of the oxidizing agent are lead tetraacetate, mercury oxide,cupric salts, etc. Among them, the use of a cupric salt in the presenceof a base such as pyridine is favorable.

Upon completion of the reaction, the reaction mixture is subjected topost-treatment such as extraction with an organic solvent orconcentration to obtain the2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide (III). Ifnecessary, purification by chromatography or recrystallization may beadopted.

The hydrazone compound (VII) can be obtained by diazotization of ananiline compound of the formula: ##STR15## wherein X and Y are each asdefined above at a temperature of -10° to 10° C. and reducing thediazotized aniline compound at a temperature of -30° to -10° C. with areducing agent such as stannous chloride to give a phenylhydrazinecompound of the formula: ##STR16## wherein X and Y are each as definedabove. This phenylhydrazine compound (IX) is then reacted with a 1.0 to1.1 equivalent amount of the cyclohexene compound (VI) in a solvent at atemperature of 0° to 100° C. for a period of 0.5 to 12 hours to give thehydrazone compound (VII). If necessary, a catalytic amount of an acidmay be present in the reaction.

As the acid, there may be used acetic acid, dilute hydrochloric acid orthe like. Examples of the solvent are methanol, ethanol, ethylene glycolmonomethyl ether, ethylene glycol, etc.

Upon completion of the reaction, the reaction mixture is subjected topost-treatment such as extraction with organic solvent or concentration.When desired, the reaction product may be purified by chromatography orrecrystallization to give the hydrazone compound (VII).

Some typical examples for production of the2-hydroxyphenyl-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide (III) areset forth below:

EXAMPLE 4

4-Chloro-2-fluoro-5-hydroxyaniline (32.5 g) was added to conc.hydrochloric acid (300 ml), and a solution of sodium nitrite (15.2 g) inwater (20 ml) was added thereto at 0° to -5° C. The resultant mixturewas stirred at 0° to 5° C. for 30 minutes, and urea was added thereto torremove excessive nitrite ion, followed by cooling to -30° C. A solutionof stannous chloride (92 g) in hydrochloric acid (160 ml) was addedthereto, and the mixture was stirred at 0° to -10° C. for 3 hours. Thereaction mixture was filtered, and the precipitated crystals weredissolved in water, neutralized with sodium hydroxide and extracted withethyl acetate. The organic layer was washed with water, dried andconcentrated. The residue was treated with ether to give4-chloro-2-fluoro-5-hydroxyphenylhydrazine (8.4 g) as crystals. Thecrystals were added to a solution of 2 -hydroxyiminocyclohexanonemorpholinoenamine (9.35 g), ethanol (90 ml) and a catalytic amount ofacetic acid and heated under reflux for 3 hours. After cooling, ethanolwas removed by evaporation, and water was added to the residue, followedby extraction with ethyl acetate. The extract was dried andconcentrated, and the residue was purified by silica gel chromatographyusing a mixture of ethyl acetate and n-hexane as an eluent to give2-(4-chloro-2-fluoro-5-hydroxyphenyl)hydrazonocyclohexanone oxime (8 g)as crystals. The crystals were suspended in a mixture of tetrahydrofuran(50 ml) and 15% pyridine-water (112 ml). A solution of cupric sulfate(CuSO₄.5H₂ O) (11.2 g) in water (40 ml) was added to the suspension,which was heated under reflux for an additional 2 hours. After cooling,water was added to the mixture, which was then extracted with ethylacetate. The organic layer was washed with an aqueous solution of cupricsulfate, dried and concentrated. The residue was purified by silica gelchromatography using a mixture of ethyl acetate and n-hexane as aneluent to give2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide(4 g) as crystals. M.P., 220°-221° C. (decomp.).

EXAMPLE 5

In the same manner as in Example 4 but using 4-chloro-3-hydroxyaniline,there was produced2-(4-chloro-3-hydroxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide.M.P., 189°-191° C. (decomp.).

On the practical usage of the benzotriazole (I) as a herbicide, it maybe applied in any preparation form such as emulsifiable concentrate,wettable powder, suspension, granules, etc. in combination with aconventional solid or liquid carrier or diluent, a surface active agentand/or an auxiliary agent.

The content of the benzotriazole (I) as the active ingredient in saidpreparation form may be usually within a range of 0.01 to 90% by weight,preferably of 0.05 to 80% by weight.

Examples of the solid carrier or diluent are fine powders or granules ofkaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite,talc, diatomaceous earth, calcite, walnut powders, urea, ammoniumsulfate, synthetic hydrated silicon dioxide, etc. As the liquid carrieror diluent, there may be exemplified aromatic hydrocarbons (e.g. xylene,methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol,celosolve), ketones (e.g. acetone, cyclohexanone, isophorone), plantoils (e.g. soybean oil, cotton seed oil), dimethylsulfoxide,acetonitrile, water, etc. The surface active agent used foremulsification, dispersion or spreading may be any of the anionic andnon-ionic type of agents. Examples of the surface active agent includealkylsulfates, alkylarylsulfonates, dialkylsulfosuccinates, phosphatesof polyoxyethylenealkylaryl ethers, polyoxyethylene alkyl ethers,polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene blockcopolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fattyacid esters, etc. Examples of the auxiliary agents includeligninsulfonates, alginates, polyvinyl alcohol, gum arabic, CMC(carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

Practical embodiments of the herbicidal composition according to theinvention are illustratively shown in the following examples whereinparts and % are by weight. The compound number of the active ingredientcorresponds to the one in Table 1.

FORMULATION EXAMPLE 1

Fifty parts of Compound No. 5 or 12, 3 parts of calcium ligninsulfonate,2 parts of sodium laurylsulfate and 45 parts of synthetic hydratedsilicon dioxide are well mixed to obtain a wettable powder.

FORMULATION EXAMPLE 2

Ten parts of Compound No. 1 or 13, 14 parts ofpolyoxyethylenestyrylphenyl ether, 6 parts of calciumdodecylbenzenesulfonate and 70 parts of cyclohexanone are well mixed toobtain an emulsifiable concentrate.

FORMULATION EXAMPLE 3

Two parts of Compound No. 6 or 14, 1 part of synthetic hydrated silicondioxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and65 parts of kaolin clay are well mixed. The mixture is then kneaded withwater, granulated and dried to obtain granules.

FORMULATION EXAMPLE 4

Twenty-five parts of Compound No. 9 or 12 is mixed with 3 parts ofpolyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose) and 69 parts of water, and the mixture is pulverized untilthe particle size of the mixture becomes less than 5 microns to obtain asuspension.

The benzotriazoles (I) thus formulated in any suitable formulation formare useful for the pre-emergence or post-emergence control of undesiredweeds by soil or foliar treatment as well as flood fallowing treatment.These treatments include the application to the soil surface prior to orafter the transplanting or the incorporation into the soil. The foliartreatment may be effected by spraying the herbicidal compositioncontaining the benzotriazoles (I) over the top of plants. It may also beapplied directly to weeds with care so as to keep the chemical off thecrop foliage.

The benzotriazoles (I) of the invention may be used together with otherherbicides to improve their activity as herbicides, and in some cases, asynergistic effect can be expected. Further, they may be applied incombination with insecticides, acaricides, nematocides, fungicides,plant growth regulators, fertilizers, soil improvers, etc.

Besides, the benzotriazoles (I) can be used as herbicides applicable toagricultural plowed field as well as paddy field. They are also usefulas herbicides to be employed for orchard, pasture land, forest,non-agricultural field, etc.

The dosage rate of the benzotriazoles (I) may vary on prevailing weatherconditions, preparation used, prevailing season, mode of application,soil involved, crop and weed species, etc. Generally, however, thedosage rate may be from 0.05 to 80 grams, preferably from 0.1 to 40grams, of the active ingredient per are. The herbicidal composition ofthe present invention prepared in the form of an emulsifiableconcentrate, a wettable powder or a suspension may ordinarily beemployed by diluting it with water at a volume of 1 to 10 liters perare, if necessary, with addition of an auxiliary agent such as aspreading agent. Examples of the spreading agent include, in addition tothe surface active agents as stated above, polyoxyethylene resin acid(ester), ligninsulfonate, abietylenic acid salt,dinaphthylmethanedisulfonate, paraffin, etc. The composition prepared inthe form of granules may be normally applied as such without dilution.

The biological effect of the benzotriazoles (I) as herbicides will beillustratively shown in the following Examples wherein the phytotoxicityto crop plants and the herbicidal activity on weeds were observedvisually as to the degree of germination as well as the growthinhibition and rated with an index 0, 1, 2, 3, 4 or 5, in which thenumeral "0" indicates that no material difference is seen in comparisonwith the untreated plant and the numeral "5" indicates the completeinhibition or death of the test plants.

The compounds shown in Table 3 below were used for comparison.

                  TABLE 3                                                         ______________________________________                                        Compound                                                                      No.     Chemical structure   Remarks                                          ______________________________________                                                 ##STR17##           Commercially available herbicide; "nitrofen"                                  1                                                B                                                                                      ##STR18##           Commercially available herbicide; "chlornitro                                 fen"                                             C                                                                                      ##STR19##           Commercially available herbicide; "bifenox"      D                                                                                      ##STR20##           Commercially available herbicide; "acifluorfe                                 n"                                               ______________________________________                                    

TEST EXAMPLE 1

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, common oat,tall morningglory and velvetleaf were sowed therein and covered withsoil. A designed amount of the test compound formulated into a wettablepowder according to Formulation Example 1 was diluted with water, andthe dilution was sprayed onto the soil surface by means of a small handsprayer at a spray volume of 10 liters per are. Thereafter, the testplants were grown in a greenhouse for 20 days, and the herbicidalactivity was examined. The results are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                                  Herbicidal activity                                                                                  Tall                                         Compound                                                                              Dosage  Japanese  Common morning-                                                                             Velvet-                               No.     (g/are) millet    oat    glory  leaf                                  ______________________________________                                        1       40      5         5      3      5                                             10      4         2      1      5                                     2       40      5         5      5      5                                             10      5         5      5      5                                     3       40      5         5      5      5                                             10      5         5      5      5                                     4       40      5         5      5      5                                             10      5         5      5      5                                     5       40      5         5      5      5                                             10      5         5      5      5                                     6       40      5         5      5      5                                             10      5         5      5      5                                     7       40      5         5      5      5                                             10      5         5      5      5                                     8       40      5         5      5      5                                             10      5         5      5      5                                     9       40      5         5      5      5                                             10      5         5      5      5                                     10      40      5         5      3      5                                             10      4         2      1      5                                     15      40      5         5      5      5                                     16      40      5         5      5      5                                             10      5         5      4      5                                     A       40      5         5      3      5                                             10      3         3      1      3                                     B       40      4         4      3      5                                             10      2         2      1      3                                     C       40      4         4      4      5                                             10      3         3      3      3                                     ______________________________________                                    

TEST EXAMPLE 2

Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filledwith upland field soil, and the seeds of Japanese millet, common oat,garden radish and velvetleaf were sowed therein and cultivated in agreenhouse for 10 days. A designed amount of the test compoundformulated into an emulsifiable concentrate according to FormulationExample 2 was diluted with water containing a spreading agent, and thedilution was sprayed onto the foliage of the test plant by means of asmall hand sprayer at a spray volume of 10 liters per are. Thereafter,the test plants were further grown in the greenhouse for 20 days, andthe herbicidal activity was examined. The results are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                  Herbicidal activity                                                 Compound                                                                              Dosage  Japanese  Common Garden Velvet-                               No.     (g/are) millet    oat    radish leaf                                  ______________________________________                                        1       20      5         3      5      5                                             5       4         3      4      5                                     2       20      5         5      5      5                                             5       5         5      5      5                                     3       20      5         5      5      5                                             5       5         5      5      5                                     4       20      5         5      5      5                                             5       5         5      5      5                                     5       20      5         5      5      5                                             5       5         4      5      5                                     6       20      5         5      5      5                                             5       5         5      5      5                                     7       20      5         5      5      5                                             5       5         5      5      5                                     8       20      5         5      5      5                                             5       5         5      5      5                                     9       20      5         5      5      5                                             5       5         5      5      5                                     10      20      5         4      5      5                                             5       4         3      4      5                                     15      20      5         4      5      5                                     16      20      5         5      5      5                                             5       4         4      5      5                                     A       20      5         4      0      5                                             5       3         2      0      3                                     B       20      5         2      3      5                                             5       3         0      0      3                                     C       20      5         3      5      5                                             5       2         3      5      5                                     ______________________________________                                    

TEST EXAMPLE 3

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of tall morningglory, cocklebur, velvetleaf, sicklepod,johnsongrass and Japanese millet as well as the seeds of wheat,sugarbeet, corn, cotton and soybean were sowed therein at a depth of 1to 2 cm. A designed amount of the test compound formulated into awettable powder according to Formulation Example 1 was diluted withwater, and the dilution was sprayed to the soil surface by means of asmall hand sprayer at a spray volume of 10 liters per are. Thereafter,the test plants were grown in a greenhouse for 20 days, and theherbicidal activity was examined. The results are shown in Table 6.

                                      TABLE 6                                     __________________________________________________________________________              Herbicidal activity                                                           Tall                                                                Compound                                                                            Dosage                                                                            morning-                                                                           Cock-                                                                             Velvet-                                                                            Sickle-                                                                           Johnson-                                                                           Japanese Sugar-     Soy-                     No.   (glare)                                                                           glory                                                                              lebur                                                                             leaf pod grass                                                                              millet                                                                             Wheat                                                                             beef                                                                              Corn                                                                             Cotton                                                                            bean                     __________________________________________________________________________    2     20  5    5   5    5   5    5    5   5   5  5   3                              5   0    5   5    4   5    5    4   5   4  3   2                        6     10  5    5   5    4   5    5    5   5   4  1   1                              2.5 --   5   5    --  5    5    4   5   2  0   0                        7     4   5    5   5    5   --   5    --  --  4  --  --                             1   5    1   5    4   --   5    --  --  3  1   0                        8     20  3    2   5    0   5    5    4   5   1  0   1                              5   0    0   4    0   5    4    2   5   0  0   0                        9     10  4    0   5    2   4    4    3   5   0  0   0                              2.5 2    0   5    0   2    2    0   4   0  0   0                        C     40  4    4   5    3   2    4    4   5   1  5   0                              10  3    2   3    0   1    3    3   5   0  0   0                        __________________________________________________________________________

TEST EXAMPLE 4

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, cotton, sugarbeet, corn and wheat as well as the seedsof tall morningglory, cocklebur, velvetleaf, sicklepod, Japanese millet,johnsongrass and green foxtail were sowed therein at a depth of 1 to 2cm. A designed amount of the test compound formulated into anemulsifiable concentrate according to Formulation Example 2 was dilutedwith water, and the dilution was sprayed to the soil surface by means ofa small hand sprayer at a spray volume of 10 liters per are. Thereafter,the test plants were grown in a greenhouse for 20 days, and theherbicidal activity was examined. The results are shown in Table 7.

                                      TABLE 7                                     __________________________________________________________________________              Herbicidal activity                                                                               Tall                                            Compound                                                                            Dosage                                                                            Soy-    Sugar-      morning-                                                                           Cock-                                                                             Velvet                                                                             Sickle-                                                                            Japanese                                                                           Johnson-                                                                           Green              No.   (glare)                                                                           bean                                                                              Cotton                                                                            beet                                                                              Corn                                                                             Wheat                                                                              glory                                                                              lebur                                                                             leaf pod  millet                                                                             grass                                                                              foxtail            __________________________________________________________________________    11    10  0   0   5   0  4    4    3   5    3    5    5    5                        2.5 0   0   3   0  3    3    2   5    --   4    3    3                  12    5   2   1   5   2  5    5    5   5    --   5    5    5                        1.25                                                                              0   0   5   0  4    4    4   5    --   5    5    5                  13    5   2   3   5   2  5    5    4   5    4    5    5    5                        1.25                                                                              0   2   5   2  3    5    --  5    --   5    5    5                  14    5   1   2   5   1  4    5    4   5    5    5    5    5                        1.25                                                                              0   0   4   0  2    4    --  5    5    5    5    5                  15    10  0   --  --  -- --   5    5   5    --   5    5    5                  16    10  --  0   --  0  --   5    5   5    --   --   5    5                  D     10  2   3   5   2  2    2    2   5    1    3    4    4                        2.5 1   2   5   0  0    1    0   4    0    2    2    2                  __________________________________________________________________________

TEST EXAMPLE 5

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of tall morningglory, cocklebur, velvetleaf, sicklepod, blacknightshade and Japanese millet as well as the seeds of wheat, sugarbeet,corn, cotton and soybean were sowed therein and cultivated for 18 days.A designed amount of the test compound formulated into an emulsifiableconcentrate according to Formulation Example 2 was diluted with watercontaining a spreading agent, and the dilution was sprayed onto thefoliage of the test plants by means of a small hand sprayer at a sprayvolume of 5 liters per are. At the time of the application, the growingstage of the test plants varied depending on their species, but theywere generally at the 1 to 4 leaf stage and in a height of 2 to 12 cm.The test plants were further grown in a greenhouse for 20 days, and theherbicidal activity was examined. The results are shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________              Herbicidal activity                                                           Tall              Black                                             Compound                                                                            Dosage                                                                            morning-                                                                           Cock-                                                                             Velvet-                                                                            Sickle-                                                                           night-                                                                            Japanese Sugar-     Soy-                      No.   (glare)                                                                           glory                                                                              lebur                                                                             leaf pod shade                                                                             millet                                                                             Wheat                                                                             beet                                                                              Corn                                                                             Cotton                                                                            bean                      __________________________________________________________________________    2     1.25                                                                              5    3   5    2   5   5    5   5   5  5   4                               0.32                                                                              3    --  5    --  5   2    3   5   4  5   3                         6     1.25                                                                              5    5   5    4   5   5    --  5   -- 5   3                               0.32                                                                              5    4   5    --  5   5    0   3   0  5   3                         7     0.32                                                                              5    4   5    4   5   5    1   5   1  5   4                               0.08                                                                              5    --  5    --  4   3    0   --  0  5   4                         8     1.25                                                                              5    3   5    2   5   5    1   3   3  5   4                               0.32                                                                              4    3   3    2   4   4    1   1   2  2   2                         9     1.25                                                                              5    3   5    3   5   5    4   5   3  5   4                               0.32                                                                              4    1   5    0   5   2    1   1   0  5   3                         15    0.32                                                                              5    5   5    4   --  --   2   --  1  --  --                              0.08                                                                              4    4   5    --  --  --   0   0   0  --  --                        C     5   5    5   5    3   5   2    3   5   3  5   5                               1.25                                                                              3    3   --   1   3   1    3   4   2  5   5                         __________________________________________________________________________

TEST EXAMPLE 8

Vats (33 cm×23 cm×11 cm) were filled with upland field soil, and theseeds of soybean, cotton, sugarbeet, corn and wheat as well as the seedsof tall morningglory, cocklebur, velvetleaf, sicklepod, redroot pigweed,Japanese millet and johnsongrass were sowed therein and cultivated for18 days in a greenhouse. A designed amount of the test compoundformulated into an emulsifiable concentrate according to FormulationExample 2 was diluted with water containing a spreading agent, and thedilution was sprayed onto the foliage of the test plants by means of asmall hand sprayer at a spray volume of 5 liters per are. At the time ofthe application, the growing stage of the test plants varied dependingon their species, but they were generally at the 1 to 4 leaf stage andin a height of 2 to 12 cm. The test plants were further grown in thegreenhouse for 20 days, and the herbicidal activity was examined. Theresults are shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________              Herbicidal activity                                                                              Tall                                             Compound                                                                            Dosage                                                                            Soy-   Sugar-      morning-                                                                           Cock-                                                                             Velvet-                                                                             Sickle-                                                                           Redroot                                                                            Japanese                                                                           Johnson-            No.   (glare)                                                                           bean                                                                             Cotton                                                                            beet Corn                                                                             Wheat                                                                             glory                                                                              lebur                                                                             leaf  pod pigweed                                                                            millet                                                                             grass               __________________________________________________________________________    11    0.32                                                                              2  3   --   0  0   4    4   5     --  5    4    4                         0.08                                                                              1  1   --   0  0   3    2   4     --  5    3    3                   12    0.08                                                                              3  4   4    3  2   5    4   5     --  5    5    5                         0.02                                                                              2  3   2    1  0   4    --  5     --  5    4    4                   13    0.08                                                                              4  4   5    1  1   5    5   5     4   5    3    3                         0.02                                                                              2  3   2    1  0   5    5   5     --  5    2    1                   14    0.32                                                                              4  4   5    2  2   5    5   5     5   5    5    4                         0.08                                                                              2  3   --   2  1   5    3   5     3   5    3    2                   D     2.5 2  3   5    4  3   5    4   2     0   5    3    2                         0.64                                                                              1  2   4    2  2   3    1   0     0   4    0    0                   __________________________________________________________________________

TEST EXAMPLE 9

Cylindrical plastic pots (diameter, 8 cm; height, 12 cm) were filledwith paddy field soil, and the seeds of barnyardgrass, broad-leavedweeds (i.e. common falsepimpernel, toothcup, waterwort) and hardstembulrush were sowed therein at a depth of 1 to 2 cm. After flooding thepots with water, the buds of arrowhead were buried in 1 to 2 cm depth,and rice seedlings at the 2-leaf stage were transplanted therein.Cultivation was carried out in a greenhouse. Six days thereafter, adesigned amount of the test compound formulated into an emulsifiableconcentrate according to Formulation Example 2 was diluted with water (5ml), and the dilution was applied to the pots by perfusion. The testplants were grown for further 20 days in the greenhouse, and theherbicidal activity was examined. The results are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                                  Herbicidal activity                                                                 Barn-                 Broad-                                  Compound                                                                              Dosage  yard-   Hardstem                                                                             Arrow- leaved                                                                              Rice                              No.     (g/are) grass   bulrush                                                                              head   weed  plant                             ______________________________________                                        1       10      5       5      --     5     1                                 2       10      5       5      5      5     --                                        2.5     5       2      5      5     0                                 3       10      5       4      --     5     1                                         2.5     4       3      --     5     0                                 4       10      5       5      --     5     1                                         2.5     4       4      --     5     0                                 5       0.63    5       5      5      5     --                                        0.16    4       4      --     5     1                                 6       0.63    5       4      5      5     0                                         0.16    5       4      --     5     0                                 7       0.63    5       4      5      5     --                                8       10      5       4      5      5     --                                        2.5     4       --     --     5     0                                 9       0.63    5       5      --     5     1                                         0.16    4       4      --     5     0                                 10      10      5       5      --     5     0                                 A       10      4       5      4      5     2                                         2.5     2       2      2      2     0                                 B       10      4       5      3      5     3                                         2.5     0       2      2      3     2                                 C       10      4       5      3      5     2                                         2.5     3       3      1      4     0                                 ______________________________________                                    

TEST EXAMPLE 10

Wagner's pots (1/5000 are) were filled with paddy field soil, and theseeds of barnyardgrass, broad-leaved weeds (i.e. common falsepimpernel,toothcup, waterwort) and hardstem bulrush were sowed therein and alsothe buds of arrowhead tided over the winter were buried in 1 to 2 cmdepth. Water was poured therein to make a flooded condition. Riceseedlings at the 3-leaf stage were transplanted to the pots. Cultivationwas carried out in a greenhouse. After three days, a designed amount ofthe test compound formulated into an emulsifiable concentrate accordingto Formulation Example 2 was diluted with water (10 ml), and thedilution was applied to the pots by perfusion, followed by addition ofwater thereto to make a 4 cm depth. The test plants were grown forfurther 20 days in the greenhouse, and the herbicidal activity wasexamined. For two days from the application, water was leaked with a 3cm depth per day. The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                                  Herbicidal activity                                                                        Barn- Broad-                                           Compound                                                                              Dosage  Rice   yard- leaved                                                                              Hardstem                                                                             Arrow-                              No.     (g/are) plant  grass weed  bulrush                                                                              head                                ______________________________________                                        11      0.4     1      5     5     4      4                                           0.1     0      5     5     3      2                                   12      0.04    0      5     5     4      --                                          0.01    0      5     5     4      --                                  13      0.04    0      5     5     4      2                                           0.01    0      4     5     3      --                                  14      0.16    --     5     5     5      4                                           0.04    0      4     5     5      3                                   15      1.25    0      5     5     5      5                                           0.32    0      5     5     5      5                                           0.08    0      5     5     5      4                                   16      1.25    0      5     5     5      4                                           0.32    0      5     5     5      4                                           0.08    0      5     5     --     --                                  B       5       0      2     4     --     2                                           2.5     0      0     1     --     1                                   ______________________________________                                    

What is claimed is:
 1. A compound of the formula: ##STR21## wherein R isa hydrogen atom, a C₁ -C₄ alkoxy group, a C₁ -C₄ alkenyloxy group, a C₃-C₄ alkynyloxy group, a C₁ -C₄ alkylthio group, adichlorocyclopropylmethoxy group or a methyldichlorocyclopropylmethoxygroup, X is a chlorine atom or a bromine atom and Y is a hydrogen atom,a fluorine atom or a chlorine atom.
 2. The compound according to claim1, wherein R is a C₁ -C₄ alkoxy group, a C₃ -C₄ alkenyloxy group or a C₃-C₄ alkynyloxy group, X is a chlorine atom or a bromine atom and Y is ahydrogen atom or a fluorine atom.
 3. The compound according to claim 1,which is2-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide.4. The compound according to claim 1, which is2-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide.5. The compound according to claim 1, which is2-(4-chloro-2-fluoro-5-allyloxyphenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide.6. The compound according to claim 1, which is2-(4-chlorophenyl)-4,5,6,7-tetrahydro-1,2,3-benzotriazol-1-oxide.
 7. Acompound of the formula: ##STR22## wherein X is a chlorine atom or abromine atom and Y is a hydrogen atom, a fluorine atom or a chlorineatom.
 8. A herbicidal composition which comprises as an activeingredient a herbicidally effective amount of the compound according toclaim 1, and an inert carrier or diluent.
 9. A method for controllingweeds which comprises applying a herbicidally effective amount of thecompound according to claim 1 to the area where the weeds grow or willgrow.
 10. The method according to claim 9, wherein the area is a soybeanfield or a rice plant field.